CN106366226A - Transition metal catalyst composition and applications thereof - Google Patents
Transition metal catalyst composition and applications thereof Download PDFInfo
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- CN106366226A CN106366226A CN201510438261.6A CN201510438261A CN106366226A CN 106366226 A CN106366226 A CN 106366226A CN 201510438261 A CN201510438261 A CN 201510438261A CN 106366226 A CN106366226 A CN 106366226A
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Abstract
The present invention discloses a transition metal catalyst composition, which comprises a main catalyst and an activator, wherein the main catalyst comprises a metallocene compound represented by a formula (I), and the activator comprises an aluminum compound and/or a boron compound. The present invention further discloses applications of the transition metal catalyst composition in preparation of polymers. According to the present invention, the storage stability and the high-temperature resistance of the composition are good, and the high molecular weight copolymer can be prepared with the composition; and with the application of the composition to prepare ethylene-alpha-olefin-non-conjugated diolefin, particularly a VNB type polymer, the ethylene-alpha-olefin-non-conjugated diolefin with characteristics of low gel content and high VNB content can be obtained. The formula (I) is defined in the specification.
Description
Technical field
The present invention relates to a kind of transition-metal catalyst compositionss and its application.
Background technology
The alkene being obtained by ethylene and one or more alpha-olefin and one or more alkadienes copolymerization is altogether
Polymers, by controlling polyethylene crystallization, can obtain the copolymer of elasticity, wherein, by ethylene, propylene
Or the elastomer copolymer that other high ' alpha ' olefin, non-conjugated diene hydrocarbon copolymerization obtain is normally referred to as
epdm.
Epdm is industrial to be typically by ethylene, propylene or other high ' alpha ' olefin, non-conjugated diene hydrocarbon
By ziegler-natta catalyzed system, prepared using solution or suspension polymerization.Ethylene, propylene
Form saturated copolymer main chain after monomer polymerization, form random rubber elastomer, in order that rubber system
Product can be vulcanized or crosslinked, introduces non-conjugated two on the saturation main chain of Propylene polymerization elastomer
Alkene, undersaturated diolefinic monomer makes epdm be provided with the crosslinking points being available for vulcanizing, and imparts product
Unique elastic and very strong heat-resisting, the resistance to ozone of product, cold-resistant and resistance to chemical attack ability, from epdm
Since realizing commercialization, its application is constantly expanded.
Business-like ethene-alpha-olefin-diene elastomer mainly passes through vanadium system homogeneous catalyst or cyclopentadienyl at present
Prepared by metallic catalyst.Domestic at present manufacturer adopt for vanadium series catalyst, for example
As disclosed in cn102863590a and cn101108885a.The appearance of metallocene catalyst makes
Polyolefin field obtains and develops rapidly.Metallocene catalyst catalyzed polyeolfin high catalytic efficiency, catalyst
Consumption is few, can simplify the removing process of remaining catalyst.Because catalyst is single-activity kind, system
Standby narrow molecular weight distribution, excellent physical properties.Metallocene catalyst can be catalyzed most of alpha-olefins with
Ethylene carries out copolymerization, the monomer that applicable traditional Ziegler-Natta catalyst can not be polymerized.But it is luxuriant
Metallic catalyst has certain limitation in terms of Molecular weight regulation.Separately there is prior art disclosure can pass through
Carry out activating metallocenes compound such as cp using promoter MAO2ticl2、cp2zrcl2、
cp2zrmecl、cp2zrme2Carry out polymerising ethylene to prepare molecular weight distribution (mw/mn) as 1.5-2.0
Polyethylene.But be difficult to obtain heavy polymer using above-mentioned catalyst system, when at 100 DEG C or
When carrying out polymerisation in solution under higher temperature, polymerization activity reduces rapidly.Therefore, this system is unsuitable for making
Standby weight average molecular weight mw is 100000 or more heavy polymer.
The prior art of domestic utilization metallocene catalyst synthesizing ethylene-alpha olefin-diene elastomer is main
There is cn101235106a, using tetramethyl-ring pentadienyl lithium and mcl4Reaction preparation
(c9h13)mcl3；Substituted indenyl lithium and (c9h13)mcl3Reaction is obtained [(c9h6r')(c9h13)]mcl2；
In the presence of catalyst metallocenes mixture and promoter MAO, with ethylene and propylene it is
Primary raw material, in 30～70 DEG C, 1～10kg/cm2Under pressure in toluene solution polyreaction 1～5h, system
Standby ethylene/propylene/diene ter-polymer rubber.
But for how preparing storage stability performance and the good catalyst of resistance to elevated temperatures and urged using this
The copolymer that agent economically and with having Commercial Prospect produces high molecular remains in the art
Important subject.
Content of the invention
The purpose of the present invention is the defect overcoming prior art, provides a kind of transition-metal catalyst combination
Thing, said composition storage stability performance and resistance to elevated temperatures are good, can be prepared using said composition
The copolymer of high molecular.Prepare ethylene-alpha-olefin-non-conjugated diene hydrocarbon using said composition, especially
The content of the gel in the polymeric articles of acquisition can be reduced during vinyl norbornene polymer, with
When can improve again vnb in polymer content that is to say, that using the present invention provide compositionss system
During standby ethylene-alpha-olefin-non-conjugated diene hydrocarbon, especially vinyl norbornene polymer, can obtain
A kind of low-gel content, the ethylene-alpha-olefin-non-conjugated diene hydrocarbon ter-polymers of high vnb content.
To achieve these goals, on the one hand, the present invention provides a kind of transition-metal catalyst combination
Thing, contains major catalyst and activator in said composition, described major catalyst is included shown in formula (i)
Metallocene compound, described activator includes aluminium compound and/or boron compound, wherein, in formula (i)
In, m is the i-th vb race element；r1、r2For the straight chained alkyl of identical or different c1-c8, c3-c8
Cycloalkyl, the aryl of c6-c12, r3、r4For the aryl of identical or different c6-c12,
The substituted aryl of c6-c12, the alkyl of c6-c12,
On the other hand, the present invention also provides a kind of transition-metal catalyst compositionss of the present invention to exist
Prepare the application in polymer.
Prepare ethylene-alpha-olefin-non-conjugated using the above-mentioned transition-metal catalyst compositionss that the present invention provides
Alkadienes, especially prepare the polymeric articles that can reduce acquisition during vinyl norbornene polymer
In gel content, the content of vnb in polymer can be improved that is to say, that using this simultaneously again
The compositionss that invention provides prepare ethylene-alpha-olefin-non-conjugated diene hydrocarbon, especially vinyl norbornene
The ethylene-alpha-olefin-non-conjugated two of a kind of low-gel content, high vnb content during polymer, can be obtained
Alkene ter-polymers.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
Bright.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, described halogen can include at least one in fluorine, chlorine, bromine and I.
In the present invention, the straight chained alkyl of described c1-c8 can include methyl, ethyl, n-pro-pyl,
At least one in normal-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
In the present invention, the cycloalkyl of described c3-c8 can include replace the cycloalkyl of c3-c8 and
The cycloalkyl of unsubstituted c3-c8, specifically can include cyclopropyl, cyclopenta, cyclohexyl, ring
Octyl group, methylcyclopropyl groups, Dimethvlcvclopropvl, ethyl cyclopropyl, diethyl cyclopropyl, methyl ring
Amyl group, dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, Dimethylcyclohexyl and ethyl ring
At least one in hexyl.In the present invention, the substituent group in the cycloalkyl of described substituted c3-c8
Can also be at least one in halogen, amino, hydroxyl and carboxyl.
In the present invention, the aryl of described c6-c12 can include phenyl, naphthyl, xenyl.
In the present invention, the substituted aryl of described c6-c12 can include p-methylphenyl, a methylbenzene
Base, to ethylphenyl, an ethylphenyl, to propyl group phenyl, a propyl group phenyl, 2,6- dimethyl benzene
Base, 2,6- diethyl phenyl, 3,5- xylyl, 2- isopropyl phenyl, 2,4,6- trimethylphenyl and
At least one in 2,4,6- triethyl group phenyl, the substituted aryl of described c6-c12 can also be included in aryl
The aryl that replaced by halogen, hydroxyl, amino and carboxyl of hydrogen atom at least one substituted replacement
Aryl, such as in the present invention it is possible to the substituted aryl exemplarily enumerating described c6-c12 also may be used
To include rubigan, to fluorophenyl, 2,4,6- trichlorophenyl, 2- methyl -4- chlorphenyl and 2- ethyl -4-
At least one in chlorphenyl.
In the present invention, the alkyl of described c6-c12 can include the alkane of the c6-c12 of straight or branched
Base, the alkyl of described c6-c12 can also include the alkyl of substituted or unsubstituted c6-c12, specifically
Ground, the alkyl of described c6-c12 can include n-hexyl, n-heptyl, n-octyl, 2- methylhexyl,
2,4,6- trimethyl, 3- methylhexyl, 3- ethylhexyl, 4- methylhexyl, 4- ethylhexyl and 2-
At least one in Methyl Octyl.
In the present invention, described aluminium compound refers to the compound containing aluminium element.
In the present invention, described boron compound refers to the compound containing boron element.
In the present invention, described vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer is as non-conjugated
Alkadienes are the polymer of vinyl norbornene.
According to an aspect of the present invention, the invention provides a kind of transition-metal catalyst compositionss, it is somebody's turn to do
Major catalyst and activator is contained, described major catalyst includes the metallocene shown in formula (i) in compositionss
Compound, described activator includes aluminium compound and/or boron compound,
Wherein, in formula (i), m is the i-th vb race element；r1、r2For identical or different c1-c8
Straight chained alkyl, the cycloalkyl of c3-c8, the aryl of c6-c12, r3、r4For identical or different
The aryl of c6-c12, the substituted aryl of c6-c12, the alkyl of c6-c12.
The described compositionss storage stability performance of the present invention and resistance to elevated temperatures are good, using said composition energy
Enough prepare the copolymer of high molecular.The above-mentioned transition-metal catalyst combination being provided using the present invention
Thing prepares ethylene-alpha-olefin-non-conjugated diene hydrocarbon, energy when especially preparing vinyl norbornene polymer
Enough contents reducing the gel in the polymeric articles obtaining, can improve vnb in polymer simultaneously again
Content is that is to say, that prepare ethylene-alpha-olefin-non-conjugated diene using the compositionss that the present invention provides
During hydrocarbon, especially vinyl norbornene polymer, a kind of low-gel content, high vnb can be obtained
The ethylene-alpha-olefin of content-non-conjugated diene hydrocarbon ter-polymers.
The compositionss being provided according to the present invention, under preferable case, in formula (i), m is selected from ti, zr
With hf element；r1、r2Identical or different, be each independently selected from c1-c6 straight chained alkyl,
The cycloalkyl of c3-c6 and phenyl；r3、r4Identical or different, it is each independently selected from containing c6-c10
Aryl, the substituted aryl of c6-c10, the alkyl of c6-c10.
The compositionss being provided according to the present invention, in formula (i), preferably described m is ti element.
The compositionss being provided according to the present invention, particularly preferably in the case of, the cyclopentadienyl shown in formula (i)
Metallic compound can include double-(cyclohexyl-cyclopentadienyl group) di-p-tolyl titanium, double-(cyclohexyl-ring
Pentadienyl) two tolyl titanium, double-(methyl-cyclopentad ienyl) di-p-tolyl titanium, double-(methyl-ring
Pentadienyl) two tolyl titanium, double-(cyclohexyl-cyclopentadienyl group) diphenyl titanium, double-(phenyl-rings penta
Dialkylene) at least one in tolyl titanium between di-p-tolyl titanium and double-(phenyl-cyclopentadienyl group) two.
In compositionss of the present invention, described activator can be aluminium compound.
According to a kind of preferred embodiment of the present invention, when described activator is aluminium compound
When, in compositionss of the present invention, the metallocene compound shown in described formula (i) is with m element
The content mol ratio that meter and described aluminium compound are counted with aluminium element is as 1:1-2000；Preferably 1:
1-200.
In compositionss of the present invention, described activator can be boron compound.
According to another kind of preferred embodiment of the present invention, when described activator is boron compound
When, in compositionss of the present invention, the metallocene compound shown in described formula (i) is with m element
The content mol ratio that meter and described boron compound are counted with boron element is as 1:0.5-100；Preferably 1:
0.5-10.
In compositionss of the present invention, described activator can be aluminium compound and boron compound.
According to another kind of preferred embodiment of the present invention, when described activator is aluminium compound
During with boron compound, in compositionss of the present invention, the metallocene chemical combination shown in described formula (i)
Thing is in terms of m element, described boron compound containing in terms of aluminium element with described aluminium compound in terms of boron element
Amount mol ratio is 1:0.1-100:10-1000；It is preferably 1:0.1-5:20-500.
According to compositionss of the present invention, described aluminium compound can be alkyl aluminum compound.
According to compositionss of the present invention, preferably described alkyl aluminum compound include MAO,
Four isobutyl aluminium alkoxides, trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three hexyls
Aluminum, dimethylaluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, two
Hexyl aluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propyl group al dichloride, isobutyl group dichloro
Change aluminum, hexyl al dichloride, dimethyl hydrogenated aluminum, ADEH, dipropyl aluminum hydride, two
At least one in isobutylaluminiumhydride and dihexyl aluminum hydride.
According to compositionss of the present invention, more preferably described aluminium compound is triethyl aluminum and/or three different
Butyl aluminum.
In compositionss of the present invention, described boron compound can include three (pentafluorophenyl group) borine,
Three (2,3,5,6- tetrafluoro phenyl) borine, three (2,3,4,5- tetrafluoro phenyl) borine, three (3,4,5- trifluorophenyl) boron
Alkane, three (2,3,4- trifluorophenyl) borine, phenyl double (pentafluorophenyl group) borine, four (pentafluorophenyl group) boric acid
Salt, four (2,3,5,6- tetrafluoro phenyl) borate, four (2,3,4,5- tetrafluoro phenyl) borate, four (3,4,5- tri-
Fluorophenyl) borate, four (2,2,4- trifluorophenyl) borate, double (pentafluorophenyl group) borate of phenyl, four
(3,5- bis trifluoromethyl phenyl) borate, ferrocene four (pentafluorophenyl group) borate, 1,1'- dimethyl two cyclopentadienyl
Ferrum four (pentafluorophenyl group) borate, four (pentafluorophenyl group) borate, trityl four (pentafluorophenyl group) boric acid
Salt, trityl four (3,5- bis trifluoromethyl phenyl) borate, triethyl ammonium four (pentafluorophenyl group) boric acid
Salt, tripropyl ammonium four (pentafluorophenyl group) borate, three (normal-butyl) ammonium four (pentafluorophenyl group) borate, three
(normal-butyl) ammonium four (3,5- bis trifluoromethyl phenyl) borate, n, n- Dimethyl Ammonium four (pentafluorophenyl group) boric acid
Salt, n, n- diethyl ammonium benzene four (pentafluorophenyl group) borate, n, n-2,4,6- pentamethyl ammonium four (pentafluorophenyl group)
Borate, n, n- Dimethyl Ammonium four (3,5- bis trifluoromethyl phenyl) borate, diisopropyl ammonium four (five fluorine
Phenyl) borate, dicyclohexyl ammonium four (pentafluorophenyl group) borate, triphenyl phosphorus four (pentafluorophenyl group) boric acid
Salt, three (aminomethyl phenyl) phosphorus four (pentafluorophenyl group) borate, three (3,5-dimethylphenyl) phosphorus four (pentafluorophenyl group) boron
Hydrochlorate and n, at least one in n- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate.
In compositionss of the present invention, preferably described boron compound include three (pentafluorophenyl group) borine,
Trityl four (pentafluorophenyl group) borate and n, in n- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate extremely
Few one kind.
In the present invention, to the preparation method of described compositionss, there is no particular limitation, art technology
Personnel can be according to routine techniquess handss well known in the art after having understood technical scheme
Major catalyst of the present invention and activator are carried out mixing and can obtain mistake of the present invention by section
Cross metal catalyst composition.
In the present invention, described major catalyst can be commercially available it is also possible to according to
Method described in cn1121274c prepares.
According to a further aspect in the invention, present invention also offers a kind of above-mentioned composition of the present invention exists
Prepare the application in polymer.
In the above-mentioned application of the present invention, the described reaction condition preparing polymer is not particularly limited
Fixed, those skilled in the art can enter according to the condition that this area routine carries out being adopted during polyreaction
Row selects.
In the present invention, in the case of particularly preferably, the condition preparing the polyreaction of polymer includes:
Pressure is 0.1-5mpa, and temperature is subzero 40 DEG C to 200 DEG C above freezing；Preferably pressure is 0.1-2mpa,
Temperature is 20-150 DEG C.
The polyreaction of the present invention be solution polymerization, those skilled in the art it will of course be appreciated that
Used in it, solvent should be in a liquid state under the polymerization conditions, and cannot participate in polyreaction,
Also the polymer that will not be obtained with reaction is reacted, and that is, this solvent is inert.This kind of solvent for
It is it will be apparent that and can easily be selected for the those of ordinary skill of polymerization field.
Even so, for the purpose of the present invention, non-polar hydrocarbon solvent can be used, this non-polar hydrocarbon solvent
Non-limiting examples are benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, ring
The combination in any of two or more in hexane or aforementioned solvents, preferably uses hexane, octane
Or heptane, hexane is more preferably used as the solvent in the polyreaction of the present invention.For the present invention's
For polyreaction, the consumption of non-polar hydrocarbon solvent is conventional, with polymer dispersity and system
Heat dispersal situations determining, the consumption of for example controllable solvent so that monomer concentration be 5-30 weight %, excellent
Elect as in the range of 8-10 weight %.
In the polyreaction of the present invention, polymerization can be terminated using terminator after completion of the polymerization reaction
Reaction.Terminator for this step is conventional to those skilled in the art.Generally permissible
The terminator using includes deionized water, alcohol, acid etc..In the present invention, it is preferred to the terminator using
For ethanol or methanol.
According to the above-mentioned application of the present invention, not special to the Adding Way of the described compositionss of the present invention
Restriction, be added in polyreaction after major catalyst and activator can be mixed in advance it is also possible to
Major catalyst and activator are added separately in polyreaction.
According to the above-mentioned application of the present invention, described polymer can include ethylene-alpha-olefin-non-conjugated diene
Hydrocarbon polymer.
Under preferable case, transition metal composition of the present invention is used for preparing non-conjugated diene hydrocarbon
During the ethylene-alpha-olefin for vinyl norbornene (vnb)-non-conjugated diene hydrocarbon polymer, can be notable
Improve the content of vnb in ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer, and reduce described ethylene-α
Gel content in alkene-non-conjugated diene hydrocarbon polymer.
In application of the present invention, in order to prepare ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer,
The consumption mol ratio of optimal ethylene monomer, alpha olefin monomers and alkadienes can be 1:0.1-4:
0.001-1；It is preferably 1:0.2-2:0.01-0.8.
In application of the present invention, preferably described alkadienes are non-conjugated diene hydrocarbon.
In application of the present invention, more preferably described alkadienes include 5- methyl -2,5- norborneol
Alkene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, vinyl norbornene (also referred to as 5-
Ethyl -2- norborene), 1,4- hexadiene, 2- methyl isophthalic acid, 4- hexadiene, 1,6- octadiene and bicyclic penta 2
At least one in alkene.
In application of the present invention, particularly preferably described alkadienes are vinyl norbornene, 5- is sub-
Ethyl -2- norborene.
In application of the present invention, described alhpa olefin can include straight containing 3-18 carbon atom
Chain or side chain alhpa olefin.
Of the present invention application in, preferably described alhpa olefin include propylene, 1-butylene, 1- amylene,
4-methyl-1-pentene, 1- hexene, 1- octene, 1-decene, 1- endecatylene, 1- dodecylene, 1- ten
At least one in four carbenes, cetene and 1- vaccenic acid.
In the polyreaction of the present invention, there is no spy to the consumption of described transition-metal catalyst compositionss
Other restriction, those skilled in the art can be selected according to the conventional amount used of catalyst, in the present invention
The consumption of preferably described transition-metal catalyst compositionss contains with the metallocene compound shown in formula (1)
The consumption weight of some m element meters and ethylene is than for 1.6 × 10-6-1.5×10-5: 1.
In ethylene-alpha-olefin of the present invention-non-conjugated diene hydrocarbon polymer, ethylene list therein
Unit, the content of non-conjugated diene hydrocarbon unit can carry out quantitative obtaining using ftir or h-nmr method
Arrive.The molecular chain conformation (mwd) of described polymer adopts waters150 gel permeation chromatography
(gpc) measure, at 135 DEG C, be measured for mobile phase with 1,2,4- trichloro-benzenes, can survey simultaneously
Number average molecular weight (mn), weight average molecular weight (mw) and mwd.The Mooney viscosity of polymer
(ml1+4125 DEG C) pass through iso289 standard test.
By the ethylene-alpha-olefin that prepared using transition-metal catalyst compositionss of the present invention-
Non-conjugated diene hydrocarbon polymer, has high vnb content, gel content is low simultaneously, and product is very suitable
Close the application such as electric wire, automobile heat-resistant tube etc. using peroxide cure.
Hereinafter will be described the present invention by embodiment.In following examples and comparative example
In, in case of no particular description, the various reagents that used are all from commercially available.In following reality
The method that applying the major catalyst in example and comparative example, being used provides all in accordance with cn1121274c is prepared into
Arrive.
In the present invention, the gel content of polymer is measured by the following method:
The polymer glue sample preparing in Example, by it in 50 DEG C of vacuum drying oven
24h is dried, weighs and be recorded as w0, then solvent is made with decahydronaphthalene and shake dissolving polymerization at 135 DEG C
Composition glue liquid sample, is filtered with the stainless (steel) wire of certain pore size (200 mesh), then will remain in rustless steel
Online undissolved polymer is dried 4h in 100 DEG C of vacuum drying oven, weighs and is recorded as
w1, calculate w1/w0× 100% draws gel content value.
In the present invention, using RUBBER ANALYSIS instrument measure angular frequency be 0.1rad/s and angular frequency be 100rad/s
When respectively the difference (δ tan δ) between the tangent of corresponding phase angle δ investigating the length of polymeric material
The content of chain branching structure, δ tan δ is bigger, closer to linear structure；Value of delta tan δ is less, branched
Structure is more, and corresponding gel content is generally higher.
Embodiment 1
The present embodiment is used for transition-metal catalyst compositionss of the present invention being described and its in preparation
Application in vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer.
Specifically, the method preparing vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer is:
1l cstr reactor (purchased from Yantai dawn precision instrument company, model 1kcf,
In similarly hereinafter), hexane is mixed with vinyl monomer, propylene monomer and vnb monomer, is then passed through
Raw material pump is delivered in polymer reactor, wherein the consumption of vinyl monomer, propylene monomer and vnb monomer
As shown in table 1.Then, will double-(cyclohexyl-cyclopentadienyl group) di-p-tolyl titanium, trityl four
(pentafluorophenyl group) sodium borate and triisobutyl aluminium are added in polymer reactor by dosing pump and carry out polymerization instead
Should, wherein, double-(cyclohexyl-cyclopentadienyl group) di-p-tolyl titanium (in terms of titanium elements), triphen first
Base four (pentafluorophenyl group) sodium borate (in terms of boron element) and the consumption of triisobutyl aluminium (in terms of aluminium element)
Mol ratio is 1:0.5:20, and, the consumption mol ratio of described compositionss and vinyl monomer is 1.5 ×
10-6: 1, temperature of reactor is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to infrared spectrometer (purchased from bruker
Company, model tensor27 type, similarly hereinafter) the polymer composition data measuring can be in the hope of corresponding monomer
Conversion ratio be listed in table 1.The viscosity of the polymer preparing, gel content and the branched situation of sign
The difference (δ tan δ) of δ tangent) it is listed in table 2.
Table 1
Table 2
Embodiment 2
The present embodiment is used for transition-metal catalyst compositionss of the present invention being described and its in preparation
Application in vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer.
The present embodiment is carried out using method same as Example 1, except that:
The transition-metal catalyst compositionss being used are double-(cyclohexyl-cyclopentadienyl group) two tolyls
Titanium and n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate, wherein, double-(cyclohexyl-cyclopentadienyl group)
Two tolyl titaniums (in terms of titanium elements) and n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate is (with boron
Element meter) consumption mol ratio be 1:0.5, and, the consumption mole of described compositionss and vinyl monomer
Than for 1.5 × 10-6: 1.The condition of described polyreaction is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Embodiment 3
The present embodiment is used for transition-metal catalyst compositionss of the present invention being described and its in preparation
Application in vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer.
The present embodiment is carried out using method same as Example 1, except that:
The transition-metal catalyst compositionss being used are double-(methyl-cyclopentad ienyl) di-p-tolyl titanium
And triethyl aluminum, wherein, double-(cyclohexyl-cyclopentadienyl group) two tolyl titanium (in terms of titanium elements)
With the consumption mol ratio of triethyl aluminum (being counted with aluminium element) as 1:1, and, described compositionss and ethylene
The consumption mol ratio of monomer is 1.5 × 10-6: 1.The condition of described polyreaction is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Embodiment 4
The present embodiment is used for transition-metal catalyst compositionss of the present invention being described and its in preparation
Application in vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer.
The present embodiment is carried out using method same as Example 1, except that:
Major catalyst in the transition-metal catalyst compositionss being used is double-(methyl-cyclopentad ienyl)
Two tolyl titaniums.Wherein, double-(methyl-cyclopentad ienyl) two tolyl titanium (in terms of titanium elements),
Trityl four (pentafluorophenyl group) sodium borate (in terms of boron element) and triisobutyl aluminium (in terms of aluminium element)
Consumption mol ratio be 1:1.2:80.The condition of described polyreaction is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Embodiment 5
The present embodiment is used for transition-metal catalyst compositionss of the present invention being described and its in preparation
Application in vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer.
The present embodiment is carried out using method same as Example 2, except that:
Major catalyst in the transition-metal catalyst compositionss being used is double-(cyclohexyl-cyclopentadiene
Base) diphenyl titanium.Wherein, double-(cyclohexyl-cyclopentadienyl group) diphenyl titanium (in terms of titanium elements) and
The consumption mol ratio of n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate (being counted with boron element) is as 1:4.5.
The condition of described polyreaction is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Embodiment 6
The present embodiment is used for transition-metal catalyst compositionss of the present invention being described and its in preparation
Application in vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer.
The present embodiment is carried out using method same as Example 3, except that:
Major catalyst in the transition-metal catalyst compositionss being used is double-(phenyl-cyclopentadienyl group)
Di-p-tolyl titanium.Wherein, double-(phenyl-cyclopentadienyl group) di-p-tolyl titanium (in terms of titanium elements)
With the consumption mol ratio of triethyl aluminum (being counted with aluminium element) as 1:30.The condition row of described polyreaction
In table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Embodiment 7
The present embodiment is used for transition-metal catalyst compositionss of the present invention being described and its in preparation
Application in vnb type ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer.
The present embodiment is carried out using method same as Example 3, except that:
Major catalyst in the transition-metal catalyst compositionss being used is double-(phenyl-cyclopentadienyl group)
Two tolyl titaniums.Wherein, double-(phenyl-cyclopentadienyl group) di-p-tolyl titanium (in terms of titanium elements)
With the consumption mol ratio of triethyl aluminum (being counted with aluminium element) as 1:80.The condition row of described polyreaction
In table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Embodiment 8
The present embodiment is carried out using method similar to Example 1.Except that:
Diolefinic monomer in the present embodiment is 5-ethylidene-2-norbornene, wherein, double-(cyclohexyl-
Cyclopentadienyl group) di-p-tolyl titanium (in terms of titanium elements), trityl four (pentafluorophenyl group) sodium borate (with
Boron element meter) and triisobutyl aluminium (being counted with aluminium element) consumption mol ratio as 1:2:40.
The property of the polymer preparing and catalysis activity (105G polymer/g titanium elements, similarly hereinafter)
It is listed in table 3.
Table 3
Embodiment 9
The present embodiment is carried out using method similar to Example 2.Except that:
Diolefinic monomer in the present embodiment is 5-ethylidene-2-norbornene, wherein, the transition that used
Metal catalyst composition is double-(cyclohexyl-cyclopentadienyl group) two tolyl titaniums, n, n- dimethyl benzene
Ammonium four (pentafluorophenyl group) sodium borate and triisobutyl aluminium.And double-(cyclohexyl-cyclopentadienyl group) two tolyl
Titanium (in terms of titanium elements), n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate (in terms of boron element) and
The consumption mol ratio of triisobutyl aluminium (being counted with aluminium element) is as 1:2:40.
The property of the polymer preparing and catalysis activity are listed in table 3.
Embodiment 10
The present embodiment is carried out using method similar to Example 3.Except that:
Diolefinic monomer in the present embodiment is 5-ethylidene-2-norbornene, wherein, the transition that used
Metal catalyst composition is double-(methyl-cyclopentad ienyl) di-p-tolyl titanium, n, n- dimethyl puratized agricultural spray
Four (pentafluorophenyl group) sodium borate and triethyl aluminum.And double-(methyl-cyclopentad ienyl) di-p-tolyl titanium (with
Titanium elements meter), n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate (in terms of boron element) and triethyl group
The consumption mol ratio of aluminum (being counted with aluminium element) is as 1:2:40.
The property of the polymer preparing and catalysis activity are listed in table 3.
Embodiment 11
The present embodiment is carried out using method similar to Example 4.Except that:
Diolefinic monomer in the present embodiment is 5-ethylidene-2-norbornene, wherein, the transition that used
Metal catalyst composition is double-(methyl-cyclopentad ienyl) two tolyl titaniums, trityl four (five fluorine
Phenyl) sodium borate and triisobutyl aluminium, and double-(methyl-cyclopentad ienyl) two tolyl titanium is (with titanium unit
Element meter), trityl four (pentafluorophenyl group) sodium borate (in terms of boron element) and triisobutyl aluminium be (with aluminum
Element meter) consumption mol ratio be 1:2:50.
The property of the polymer preparing and catalysis activity are listed in table 3.
Embodiment 12
The present embodiment is carried out using method similar to Example 5.Except that:
Diolefinic monomer in the present embodiment is 5-ethylidene-2-norbornene, wherein, the transition that used
Metal catalyst composition is double-(cyclohexyl-cyclopentadienyl group) diphenyl titanium, n, n- dimethyl puratized agricultural spray four
(pentafluorophenyl group) sodium borate and triisobutyl aluminium, and double-(cyclohexyl-cyclopentadienyl group) diphenyl titanium is (with titanium
Element meter), n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate (in terms of boron element) and triisobutyl aluminium
The consumption mol ratio of (being counted with aluminium element) is as 1:2:40.
The property of the polymer preparing and catalysis activity are listed in table 3.
Embodiment 13
The present embodiment is carried out using method similar to Example 6.Except that:
Diolefinic monomer in the present embodiment is 5-ethylidene-2-norbornene, wherein, the transition that used
Metal catalyst composition is double-(phenyl-cyclopentadienyl group) di-p-tolyl titanium, n, n- dimethyl puratized agricultural spray
Four (pentafluorophenyl group) sodium borate and triethyl aluminum, and double-(phenyl-cyclopentadienyl group) di-p-tolyl titanium (with
Titanium elements meter), n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate (in terms of boron element) and triethyl aluminum
The consumption mol ratio of (being counted with aluminium element) is as 1:2:60.
The property of the polymer preparing and catalysis activity are listed in table 3.
Embodiment 14
The present embodiment is carried out using method similar to Example 7.Except that:
Diolefinic monomer in the present embodiment is 5-ethylidene-2-norbornene, wherein, the transition that used
Metal catalyst composition is double-(phenyl-cyclopentadienyl group) two tolyl titaniums, n, n- dimethyl puratized agricultural spray
Four (pentafluorophenyl group) sodium borate and triethyl aluminum, and double-(phenyl-cyclopentadienyl group) two tolyl titanium (with
Titanium elements meter), n, n- dimethyl puratized agricultural spray four (pentafluorophenyl group) sodium borate (in terms of boron element) and triethyl aluminum
The consumption mol ratio of (being counted with aluminium element) is as 1:2:50.
The property of the polymer preparing and catalysis activity are listed in table 3.
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that:
The catalyst being used is not the compositionss of the present invention, but the vanadium oxytrichloride-sesquialter alkyl using
Aluminum (ziegler natta catalyst), and, the ziegler natta catalyst used in this comparative example
Consumption with identical in embodiment 1.The condition of described polyreaction is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Comparative example 2
This comparative example is carried out using method similar to Example 2, except that:
The catalyst being used is not the compositionss of the present invention, but the dicyclopentadiene two using is to first
Phenyl titanium that is to say, that used in this comparative example catalyst be only conventional metallocene catalyst and
Do not contain activator of the present invention.And, the dicyclopentadiene two used in this comparative example is right
The consumption of tolyl titanium with identical in embodiment 2.The condition of described polyreaction is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Comparative example 3
This comparative example is carried out using method similar to Example 5, except that:
The catalyst being used is not the compositionss of the present invention, but use
[c5h4-sime2-n(t-bu)]ticl2(the luxuriant System Catalyst of constrained geometry configuration).And, this contrast
The luxuriant System Catalyst of the constrained geometry configuration used in example is identical with the consumption in embodiment 5.Described
The condition of polyreaction is listed in table 1.
On reactor discharging pipeline, continuous collected polymer solution carries out solvent removal and obtains solid polymerization
Thing, is vacuum dried and weighs, and obtains polymer yield data, according to the polymerization of determination of infrared spectroscopy
Thing composition data can be listed in table 1 in the hope of the conversion ratio of corresponding monomer.The polymer preparing viscous
The difference (δ tan δ) of degree, gel content and the δ tangent characterizing branched situation is listed in table 2.
Comparative example 4
This comparative example is carried out using method similar to Example 8, except that:
The compositionss for dicyclopentadiene titanium chloride rather than the present invention of the catalyst being used.And
And, the use of the dicyclopentadiene titanium chloride used in this comparative example and the major catalyst in embodiment 8
Amount is identical.
The property of the polymer preparing and catalysis activity are listed in table 3.
Comparative example 5
This comparative example is carried out using method similar to Example 9, except that:
The major catalyst of the catalyst being used is dicyclopentadiene diphenyl titanium.Rather than the present invention
Compositionss.And, the master in the dicyclopentadiene diphenyl titanium used in this comparative example and embodiment 9
The consumption of catalyst is identical.
The property of the polymer preparing and catalysis activity are listed in table 3.
Result from above-mentioned table 1-3 can be seen that the polymer preparing in embodiments of the invention
In vnb content high and gel content is low, and used in comparative example 1, catalyst is conventional neat
Ge Le-Natta-catalyzed System Catalyst, contains only 0.91% vnb, far in the polymer preparing
Less than the result in embodiments of the invention, and gel content be 10 times of embodiments of the invention with
On, degree of branching is also higher.It is conventional cyclopentadienyl catalyst used in comparative example 2, make in comparative example 3
For the cyclopentadienyl catalyst of constrained geometry configuration, can also from the result of comparative example 2 and comparative example 3
Go out, in its polymer preparing, vnb content is very low, and conversion ratio is extremely low, and gel content is very
High.
The result of contrast embodiments of the invention 8-14 and comparative example 4-5 can be seen that using institute of the present invention
The compositionss stated can prepare the polymer of high molecular, and, the catalysis of embodiments of the invention
The activity of agent is apparently higher than the catalysis activity of catalyst in comparative example.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention no longer separately illustrates to various possible compound modes.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of transition-metal catalyst compositionss, contain major catalyst and activator in said composition,
Described major catalyst includes the metallocene compound shown in formula (i), and described activator includes aluminium compound
And/or boron compound,
Wherein, in formula (i), m is the i-th vb race element；r1、r2For identical or different c1-c8
Straight chained alkyl, the cycloalkyl of c3-c8, the aryl of c6-c12, r3、r4For identical or different
The aryl of c6-c12, the substituted aryl of c6-c12, the alkyl of c6-c12.
2. compositionss according to claim 1, wherein, in formula (i), m is selected from ti, zr
With hf element；r1、r2Identical or different, be each independently selected from c1-c6 straight chained alkyl,
The cycloalkyl of c3-c6 and phenyl；r3、r4Identical or different, it is each independently selected from the virtue of c6-c10
Base, the substituted aryl of c6-c10, the alkyl of c6-c10.
3. compositionss according to claim 2, wherein, the metallocene compound shown in formula (i)
Including double-(cyclohexyl-cyclopentadienyl group) di-p-tolyl titanium, double-(cyclohexyl-cyclopentadienyl group) two first
Phenyl titanium, double-(methyl-cyclopentad ienyl) di-p-tolyl titanium, double-(methyl-cyclopentad ienyl) two first
Phenyl titanium, double-(cyclohexyl-cyclopentadienyl group) diphenyl titanium, double-(phenyl-cyclopentadienyl group) two pairs toluene
At least one in tolyl titanium between base titanium and double-(phenyl-cyclopentadienyl group) two.
4. the compositionss according to any one in claim 1-3, wherein, described activator is
Aluminium compound, and the metallocene compound shown in described formula (i) in terms of m element with described aluminium compound
The content mol ratio counted with aluminium element is as 1:1-2000；It is preferably 1:1-200.
5. the compositionss according to any one in claim 1-3, wherein, described activator is
Boron compound, and the metallocene compound shown in described formula (i) in terms of m element with described boron compound
The content mol ratio counted with boron element is as 1:0.5-100；It is preferably 1:0.5-10.
6. the compositionss according to any one in claim 1-3, wherein, described activator is
Aluminium compound and boron compound, and the metallocene compound shown in described formula (i) is in terms of m element, institute
State boron compound and count the content mol ratio counted with aluminium element with described aluminium compound with boron element for 1:
0.1-100:10-1000；It is preferably 1:0.1-5:20-500.
7. the compositionss according to any one in claim 1-3, wherein, described aluminium compound
Including alkyl aluminum compound；
Preferably described alkyl aluminum compound includes MAO, four isobutyl aluminium alkoxides, trimethyl
Aluminum, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three hexyl aluminum, dimethylaluminum chloride, diethyl
Base aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, dihexylaluminum chloride, methyl dichloro
Aluminum, ethylaluminum dichloride, propyl group al dichloride, isobutyl aluminium dichloride, hexyl al dichloride, two
Dimethyl aluminum hydride, ADEH, dipropyl aluminum hydride, diisobutyl aluminium hydride and dihexyl hydrogen
Change at least one in aluminum；
More preferably described aluminium compound is triethyl aluminum and/or triisobutyl aluminium.
8. the compositionss according to any one in claim 1-3, wherein, described boron compound
Including three (pentafluorophenyl group) borine, three (2,3,5,6- tetrafluoro phenyl) borine, three (2,3,4,5- tetrafluoro phenyl) boron
Double (pentafluorophenyl group) boron of alkane, three (3,4,5- trifluorophenyl) borine, three (2,3,4- trifluorophenyl) borine, phenyl
Alkane, four (pentafluorophenyl group) borate, four (2,3,5,6- tetrafluoro phenyl) borate, four (2,3,4,5- phenyl tetrafluorides
Base) borate, four (3,4,5- trifluorophenyl) borate, four (2,2,4- trifluorophenyl) borate, phenyl be double
(pentafluorophenyl group) borate, four (3,5- bis trifluoromethyl phenyl) borate, ferrocene four (pentafluorophenyl group) boron
Hydrochlorate, 1,1'- dimethyl ferrocene four (pentafluorophenyl group) borate, four (pentafluorophenyl group) borate, triphen
Methyl four (pentafluorophenyl group) borate, trityl four (3,5- bis trifluoromethyl phenyl) borate, three second
Base ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (pentafluorophenyl group) borate, three (normal-butyl) ammonium four
(pentafluorophenyl group) borate, three (normal-butyl) ammonium four (3,5- bis trifluoromethyl phenyl) borate, n, n- diformazan
Base ammonium four (pentafluorophenyl group) borate, n, n- diethyl ammonium benzene four (pentafluorophenyl group) borate, n, n-2,4,6-
Pentamethyl ammonium four (pentafluorophenyl group) borate, n, n- Dimethyl Ammonium four (3,5- bis trifluoromethyl phenyl) boric acid
Salt, diisopropyl ammonium four (pentafluorophenyl group) borate, dicyclohexyl ammonium four (pentafluorophenyl group) borate, three
Phenyl phosphorus four (pentafluorophenyl group) borate, three (aminomethyl phenyl) phosphorus four (pentafluorophenyl group) borate, three (diformazans
Base phenyl) phosphorus four (pentafluorophenyl group) borate and n, in n- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate
At least one；
Preferably described boron compound includes three (pentafluorophenyl group) borine, trityl four (pentafluorophenyl group) boric acid
Salt and n, at least one in n- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate.
9. application in preparing polymer for the compositionss described in any one in claim 1-8.
10. application according to claim 9, wherein, described polymer include ethylene-alpha-olefin-
Non-conjugated diene hydrocarbon polymer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108126753A (en) * | 2017-12-26 | 2018-06-08 | 华东理工大学 | Application of a kind of metallocene compound in Allyl end groups oligomerization of propene object is prepared |
| CN108864348A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer and preparation method thereof |
| CN110387003A (en) * | 2018-04-20 | 2019-10-29 | 中国石油化工股份有限公司 | Polyolefin elastomer and preparation method thereof |
| CN111868116A (en) * | 2018-03-20 | 2020-10-30 | 三井化学株式会社 | Ethylene-alpha-olefin-nonconjugated polyene copolymer, process for producing the same, and use thereof |
| WO2023226318A1 (en) * | 2022-05-27 | 2023-11-30 | 中国石油化工股份有限公司 | Metallocene complex and preparation method therefor, catalyst composition, olefin polymerization method and olefin polymer |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0841081A (en) * | 1994-05-25 | 1996-02-13 | Asahi Chem Ind Co Ltd | New titanocene compound, catalyst composition for hydrogenating olefin compound and method for hydrogenating olefin compound using the same catalyst composition |
| CN1178222A (en) * | 1996-06-06 | 1998-04-08 | 联合碳化化学品及塑料技术公司 | Process for controlling static in polymerizations utilizing metallocene catalysts |
| CN1214699A (en) * | 1996-03-27 | 1999-04-21 | 陶氏化学公司 | Highly soluble olefin polymerization catalyst activator |
| CN1219178A (en) * | 1996-04-01 | 1999-06-09 | 陶氏化学公司 | Olefin solution polymerization |
| CN1373008A (en) * | 2001-02-28 | 2002-10-09 | 北京燕山石油化工公司研究院 | Metallocene catalyst and its preparing process, application and selective hydrogenation process |
| CN100389129C (en) * | 1996-04-10 | 2008-05-21 | 尤尼罗亚尔化学公司 | Polymerization process for polyolefin elastomer production, cation-forming cocatalyst for activation of metallocene procatalyst, and polyolefin elastomer |
| CN101389667A (en) * | 2005-12-30 | 2009-03-18 | 北方技术股份有限公司 | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
| EP2272588B1 (en) * | 2009-06-22 | 2013-06-12 | Dynasol Elastomeros, S.A. | Catalyst for the hydrogenaton of unsaturated compounds |
| CN104718026A (en) * | 2012-09-21 | 2015-06-17 | 旭化成化学株式会社 | Hydrogenation catalyst composition and hydrogenation method using said hydrogenation catalyst composition |
-
2015
- 2015-07-23 CN CN201510438261.6A patent/CN106366226B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0841081A (en) * | 1994-05-25 | 1996-02-13 | Asahi Chem Ind Co Ltd | New titanocene compound, catalyst composition for hydrogenating olefin compound and method for hydrogenating olefin compound using the same catalyst composition |
| CN1214699A (en) * | 1996-03-27 | 1999-04-21 | 陶氏化学公司 | Highly soluble olefin polymerization catalyst activator |
| CN1219178A (en) * | 1996-04-01 | 1999-06-09 | 陶氏化学公司 | Olefin solution polymerization |
| CN100389129C (en) * | 1996-04-10 | 2008-05-21 | 尤尼罗亚尔化学公司 | Polymerization process for polyolefin elastomer production, cation-forming cocatalyst for activation of metallocene procatalyst, and polyolefin elastomer |
| CN1178222A (en) * | 1996-06-06 | 1998-04-08 | 联合碳化化学品及塑料技术公司 | Process for controlling static in polymerizations utilizing metallocene catalysts |
| CN1373008A (en) * | 2001-02-28 | 2002-10-09 | 北京燕山石油化工公司研究院 | Metallocene catalyst and its preparing process, application and selective hydrogenation process |
| CN101389667A (en) * | 2005-12-30 | 2009-03-18 | 北方技术股份有限公司 | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
| EP2272588B1 (en) * | 2009-06-22 | 2013-06-12 | Dynasol Elastomeros, S.A. | Catalyst for the hydrogenaton of unsaturated compounds |
| CN104718026A (en) * | 2012-09-21 | 2015-06-17 | 旭化成化学株式会社 | Hydrogenation catalyst composition and hydrogenation method using said hydrogenation catalyst composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864348A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer and preparation method thereof |
| CN108864348B (en) * | 2017-05-15 | 2021-02-05 | 中国石油化工股份有限公司 | Ethylene-alpha olefin-non-conjugated diene polymer and preparation method thereof |
| CN108126753A (en) * | 2017-12-26 | 2018-06-08 | 华东理工大学 | Application of a kind of metallocene compound in Allyl end groups oligomerization of propene object is prepared |
| CN111868116A (en) * | 2018-03-20 | 2020-10-30 | 三井化学株式会社 | Ethylene-alpha-olefin-nonconjugated polyene copolymer, process for producing the same, and use thereof |
| CN111868116B (en) * | 2018-03-20 | 2022-12-09 | 三井化学株式会社 | Ethylene-alpha-olefin-nonconjugated polyene copolymer, process for producing the same, and use thereof |
| CN110387003A (en) * | 2018-04-20 | 2019-10-29 | 中国石油化工股份有限公司 | Polyolefin elastomer and preparation method thereof |
| CN110387003B (en) * | 2018-04-20 | 2022-03-01 | 中国石油化工股份有限公司 | Polyolefin elastomer and preparation method thereof |
| WO2023226318A1 (en) * | 2022-05-27 | 2023-11-30 | 中国石油化工股份有限公司 | Metallocene complex and preparation method therefor, catalyst composition, olefin polymerization method and olefin polymer |
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